Lubricants containing melamine derivatives



3,27%,436 LUBRICANTS CONTAlNlNG MELAMHNE DERIVATIVES Joachim Dazzi, Riehen, near Basel, and Ernst Keller, Binningen, near Basel, Switzerland, assignors to J. R. Geigy, A.G., Basel, Switzerland No Drawing. Original application Jan. 3, 1963, Ser. No. 249,119. Divided and this application Mar. 21, 1963, Ser. No. 266,828 Claims priority, application Switzerland July 7, 1961,

Claims. c1. 2s2-s0 This application is a continuation-in-part of our copending application Ser. No. 208,124, filed July 6, 1962 (abandoned since the filing of the present application). This application is a division of application Serial No. 249,119, filed January 3, 1963.

The present invention concerns the use of N,N',N- substituted melamine derivatives which contain more than one 1,3,5-triazine ring in the molecule as lubricants, dielectric media and functional fluids. The term functional fluids as used in this specification is meant to designate media employed to transfer mechanical and/ or thermal energy which are fluid under the conditions of temperature and pressure at which they perform their intended function. As such the term includes hydraulic as well as heat transfer media.

The invention also concerns compositions of matter which contain at least one melamine derivative having more than one 1,3,5-triazine ring and at least one further substance from the series consisting of highly purified mineral oils, synthetic lubricant oils of an ester basis, silicone oils, antioxidants, thickeners, agents lowering the solidfication point, high pressure additives and anticorrosives. In a preferred aspect of this invention, the melamine derivatives amount to from about 5 to 95% by weight of the said composition.

Very high demands with regard to heat and oxygen stability are made of synthetic lubricating agents and functional fluid-s such as are used, for example, in apparatuses and engines operating at high temperatures.

For such uses, synthetic lubricating agents and func tional fluids must, in the first place, fulfill the following conditions:

(1) They must be capable of forming a lubricating film on the most various metals;

(2) They must have "substantial stability to heat and must be difficult to volatilize;

(3) They should have a high flash point;

(4) They should not form any acid decomposition products;

(5) They should retain their mechanical, electrical and/ or lubricating properties over as wide a temperature range as possible, e.g., their viscosity should be as little dependent as possible on temperature;

(6) They should have, in addition to these properties, as low a solidification point as possible.

It is difficult to find substances which fulfill these demands to such an extent that they can be employed as lubricants and/or functional fluids for high temperature engines.

It has now surprisingly been found that certain melamines suitably substituted at the nitrogen atom of the amino groups and which contain more than 1,3,5-triazine ring in the molecule have many of the properties required above and thus can be used as functional fluids when high demands are made and as synthetic lubricants. The disinguishing characteristic of these new melamine derivatives is the presence of more than one 1,3,5-triazine ring in the molecule and the substitution of all amino groups nited States Patent 0 by hydrocarbon radicals, advantageously by saturated hydrocarbon radicals, which may have inert substituents.

The melamine derivatives according to the invention are produced by reacting an organic polyamine having two or more acylatable amino groups, an amount of cyanuric halide which is equimolar to the number of its acylatable amino groups, and an amount which is double the equimolecular amount of this number of primary and/or secondary amines having aliphatic, araliphatic, alicyclic and monoor poly-nuclear aromatic nitrogen substituents, which substituents may be further inertly substituted, and wherein the two nitrogen substituents of the secondary amine group can be bound to each other direct or can be bound by way of hetero atoms to form a ring. The reaction is performed in steps in any order desired under the usual conditions and in the presence of acid binding agents to form the corresponding N,N,N"-substituted melamine compounds having several 1,3,5-triazine rings and the components are advantageously so chosen that each 1,3,5-triazine ring contains at most one arylamino group.

A preferred method consists in reacting the organic polya-mine having two or more acylatable amino groups with an amount equimolecular to the number of its acylatable amino groups of 6-halogen-2,4-diamino-1,3,5- triazines. These triazines are produced from a cyanuric halide by a method known per se by reacting it stepwise with 2 mols of primary and/ or secondary aliphatic, araliphatic, alicyclic and saturated-heterocyclic amine, or they are produced from one mol of such an amine and one mol of a monoor poly-nuclear aromatic amine in which all nitrogen substituents may have further inert substituents.

Advantageously polyamines of saturated or partly satu rated hydrocarbon radicals which may contain inert substituents and heteroatoms as chain, bridging or ring members are used in the process according to the invention as organic amines having two or more acylatable amino groups. However, they can also contain aromatic rings and especially one or more preferably uncondensed aromatic rings. In addition they can contain hetero rings or can consist of hetero rings; in this case they are advantageously saturated or at least partly saturated hetero rings.

Examples of polyamines usable according to the invention are: alkylene diand poly-amines such as ethylenediamine, 1,2- or 1,3-propylenediamine, 1,4-, 1,3- or 2,3- butylenediarnine, 1,6-hexylenediamine, 1,10-decylenediamine, 1,18-octadecylenediamine, 1,2,3-triaminopropane, N,N bis-aminoethyl or N,N-bis-aminopropyl-alkylamines, -cycloalkylamines, -aralkylamines, and -phenylamines, diethylenetriamine, triethylenetetramine, tetraethylenepentamine; ether amines such as {3,B'-diaminodiethyl ether, B,,8- or y,'y'-diaminodipropyl ether, ,8,B'-diaminodiethyl glycol ether, fl,,8-diaminodiethyl sulphide, ,v-dia'minodipropyl sulphide, 4,4-diaminodip'henyl ether, 1,3- or 1,4bis-'y-aminopropoxybenzene, 1,2-bis-p-aminophenoxyethane, bis-(4-'y-aminopropoxyphenyl)-alkanes and -cycloalkanes such as 2,2-bis-(4, -anrinopropoxyphenyl)-propane or 2,2-bis-(4, -aminopropoXyphenyl)-butane, or 1,1- bis-(4,y-aminopropoxyphenyl)-cyclohexane, 4,4'-diaminodiphenyl sulphide; aralkylenediamines such as 1,3- or 1,4- bis-aminornethylbenzene; cycloalkylenediamines such as 1,2- or 1,4-diaminocyclohexane, 4,4-diaminodicyclohexyl, bis (4-aminocyclohexyl)-methane, 2,2-bis-(4-aminocyclohexyl)-propane or -butane, or 1,1-bis-(4-aminocyclohexyl)-cyclohexane; aromatic diamines such as 4,4-di aminodiphenyls, 4,4'-diaminodiphenylmethanes, bis-4- aminophenylalkanes or -cycloalkanes such as 2,2-bis-(4'- aminophenyl)-propane or -butane, 1,l-bis-(4'-aminophenyl)-cyclohexane e-tc., heterocyclic polyamines e.g. diazines such as piperazine, 2,5-dimethylpiperazine, 2,3,5,6-tetramethylpiperazine, l-fi-aminoethyh, 1,;3-aminopropylor l -aminopropylpiperazine, 1,4-bis-fi-aminoethyl piperazine or 1,4-bis-y-aminopropyl piperazine. Examples of inert substituents of the organic radicals of these and similar compounds are alkoxy groups, alkyhnercapto groups, aromatic radicals and also halogen such as fiuorine, chlorine or bromine, alicyclic, aromatic and saturated heterocyclic radicals, also alkyl groups such as methyl, ethyl, propyl, isopropyl, tert. butyl, tert. amyl, iso-octyl, nonyl, dodecyl groups etc.

As amino compounds having only one acylatable amino group are used in the process according to the invention primary or secondary amino compounds having aliphatic, alicyclic araliphatic or aromatic groups, in this case advantageously with monoor poly-nuclear but not with condensed aromatic groups, or saturated or partly saturated nitrogen rings such as pyrrolidine, piperidine, hexamethyleneimine, morpholine and N-monoalkylor N-monoaralkyl-piperazines etc. Also in these amines, the organic nitrogen substituents can contain further inert substituents; for example, aliphatic radicals may contain alkoxy, alkylmercapto, phenoxy or phenylmercapto groups; cyclic and aromatic groups may contain alkyl substituents, and aromatic rings may further contain halogen such as fluorine, chlorine or bromine. Advantageously the nitrogen substituents of primary and secondary amines used according to the invention are saturated or partly saturated radicals, for example normal or branched chain alkyl groups with 1 to 20 carbon atoms, cycloalkyl radicals such as cyclopentyl, cyclohexyl or alkylcyclopentyl radicals, tetrahydroor decahydro-naphthyl radicals, abiethyl or dihydroabiethyl radicals.

Dialkylamines having 4 to 36 carbon atoms are particularly suitable for reducing the melting or solidification point of the end products. For example, diethylamine, di-n-butylamine, dihexylamine, di-Z-ethyl-hexylamine, din-octylamine, di-n-decylamine, bis-n-dodecylamine, bis-nhexadecylamine, bis-n-octadecylamine or dicyclohexylamine are employed. In addition to the monoor polynuclear, advantageously non-condensed aromatic radicals, aromatic amines contain, for example in addition to the phenyl, monomethylphenyl, or dimethylphenyl, trimethylphenyl, 2,6-dibutylphenyl, 2,6-di-t-arnyl-4-methylphenyl, diphenyl, benzylp'henyl, phenoxyphenyl or phenyhnercaptophenyl radical, as further nitrogen substituents preferably a lower alkyl group, e.g. the methyl, ethyl, or nbutyl group.

The preferably used 2,4-bis-alkylamino-6-chloroor or -6-b-romo-1,3,5-triazines, which are known because of their herbicidal action, are obtained by methods known per se by reacting two of the halogens of the cyanuric halide in the cold or at a moderately raised temperature with 2 mols of primary or 2 mols of secondary or 1 mol of primary and 1 mol of secondary monoamine. The reaction is performed in the presence of acid binding agents, possibly in inert organic solvents or diluents such as acetone, methylethylketone, dioxan, tet-rahydrofurane, benzene, toluene, xylenes, chlorobenzene etc. The reaction of the third halogen with an acylata-ble amine is performed advantageously in the presence of pulverized caustic alkalies, at a raised temperature of, e.g. 80 to 240 C., either in the melt f the components or in an inert, anhydrous organic solvent e.g. in one of the aromatic solvents given above. It is advantageous if the first and/or the second halogen of the cyanuric halide is reacted with less reactive amines and the third halogen is reacted with an easily reacting amino group. In the first and second steps of the reaction of the cyanuric halide, also alkali metal salts of low fatty acids or alkali metal salts of polybasic, weaker inorganic acids, e.g. sodium or potassium carbonates, sodium or potassium bicarbonates, sodium or potassium acetates, t-rialkali metal salts of o-phosphoric acid and, in suitable form and amount, also alkali hydroxides as well as tertiary nitrogen bases such as pyridine, picolines,

triethylamine or triethanolamine can be used as acid binding agents. In the last step of the halogen reaction of the triazine, instead of the acid binding agents memtioned, also an excess of the amine to be reacted can 'be used as acid binding agent. Further details regarding the reaction conditions can be seen from the following examples.

The melamine derivatives containing several 1,3,5-triazine rings are of the formula In this formula, A is an n-valent polyamine radical having from 2 to 20 carbon atoms and a total of from n to 5 nitrogen atoms, all of which are acylatable and separated from each other by at least 2 carbon atoms, and pertaining to the class consisting of the radicals of (a) Saturated chain-linked, cyclic and mixed chain-linked-and-cyclic polyamines,

(b) Saturated chain-linked aliphatic polyatmines which contain oxygen in the chain, and

(c) Phenyl-cycl0hexylene-phenyl-diamines,

n is a positive integer ranging from 2 to 5, and each one of the two to five right hand moieties in the above formula is linked to one of the said acylatable nitrogen atoms of A.

Each of R and R is independently of the other either hydrogen or an alkyl group with maximally 18 carbon atoms.

Each of R and R is independently of the other an alkyl group with maximally 18 carbon atoms, a monocyclic aralkyl group, the .alkylene bridge of which, linked to the nitrogen atom at which R and/or R is substituted, has maximally 4 carbon atoms, further, an unsubstituted benzene radical or a benzene radical substituted with chlorine, fluorine, bromine or alkyl with maximally 12 carbon atoms.

R and R taken together, on the one hand, and/or R and R taken together on the other hand, can be joined to form, together with the nitrogen to which they are attached, a tetramethyleneimino, pentamethyleneimino, hexamethyleneimino, morpholino or n-methylpireperazino radical.

The term polyamine radical as used in the instant specification and claims means the radical derived from an organic amine which has more than one and preferably two terminal -NH group and may have from one to three -NH- members interrupting a straight, branched or cyclic chain of carbon atoms. Branched triamines are also comprised by this term.

Cyclic polyamine radicals are, for instance, the piperazine radical and the methyl piperazine radicals; mixed chain-and-cyclic polyamine radicals are those in which the a-cylatable amino groups are attached to, or incorporated (as NH or N) in a saturated aliphatic nucleus which consists of a straight and/or branched carbon atom sequence as well as saturated cyclic configurations of six carbon atoms per cycle. The chain-linked portions of the aliphatic nucleus are attached to the cyclic portions preferably in por 0- position rleative to each other.

A prefered configuration A of the moiety A in the above Formula I corresponds to the formula in which each of m, p and q is an integer ranging from 1 to 2, each of Q Q Q and Q taken independently is an alkylen'e group the number of carbon atoms of which is at least two and such that the total number of carbon atoms in A does not exceed 20; of course, in the whole molecule (Formula I), n is 2 to 5 and the total number of nitrogen atoms is again at least 2 but not more than 5, all of the nitrogen atoms being acylatable and separated by at least two carbon atoms from one another; R R R and R have the same meaning as stated in connection with Formula I above.

Each of R and R is either hydrogen, or an alkyl radical of maximally 18 carbon atoms, and R and R taken together can be either CH CH or GH OH- or OH-C11 H3 (III-I3 CH3 if m=p=q=l. In this case Q has the same meaning as R and R taken together.

Another configuration, A comprised by A in Formula I, which is to be found in compounds of good properties, is that of diamino radicals of the formula in which radical the oxygen and/or nitrogen atoms are separated by at least two carbon atoms from one another, k being an integer ranging from 2 to 4; these are therefore, radicals of chain-linked diamines in which the chain of carbon atoms is interrupted by from one to four oxygen atoms.

Q Q Q R and R have the same meanings as given above. Of course, in this case, n in Formula I must be 2. Again, the total number of carbon atoms of A must not exceed 20.

In a further class of functional fluids according to the invention, the moiety A of Formula I is represented by the radical A of cyclic or a mixed chain linked-andcyclic diamine, which radical has the formula in which Q and Q have the meaning given above, a, e and f are each an integer ranging from 1 to 2, and each of Z and Z taken independently, are either cyclohexylene or methyl cyclohexylene.

Of course, in this case, n in Formula I must be 2; R R R and R have the meanings given above, and the total number of carbon atoms of A must not exceed 20.

Another group of compounds are characterized by an A moiety which is a phenyl-cyclohexylene-phenyl diamine, preferably with the two amino groups in 4, 4'- position at the phenyl nuclei.

The melamine derivatives produced according to the invention can contain mixtures of primary, secondary and tertiary amines. Because of their great heat stability, they can easily be obtained in pure form by distillation 1n a high vacuum. They can also be purified by extraction with a selective solvent such as acetic acid, by treatment with a bleaching earth such as Tonsil AC or an adsorptive earth such as Celite PC or with an ion exchanger such as Amberlite IR-120.

The melamine derivatives according to the invention are, at room temperature, either liquid, semi-solid fatty or waxy, non-crystalline or crystalline substances which are excellently thermostable and of low vapor-pressure.

Depending upon their properties such as their viscositytemperature relationship, their heat capacity, coefiicient of heat transfer etc., the melamine derivatives are useful in many applications. The more important ones are as lubricants for parts of machines performing heavy duty at high temperatures, as safety lubricants for incorporation in bearings made of sintered metals or thermosetting resins, as waterproof sealing agents for porous surfaces such as wooden tiles and as heat transfer agents for heat exchangers operating at high temperatures.

Their advantage is the unusual combination of valuable properties such as high thermal stability, low volatility, high flash point, chemical inertness, low tendency for metallic corrosion and their ability to form lubricant films.

In particular, the very good stability to acid and alkali of the melamine derivatives according to the invention is remarkable. In a liquid condition they are distinguished by medium to high viscosity.

The melamines according to the invention can be used as lubricants in many ways. Properties desired for a particular purpose can also be obtained by producing suitable mixtures of these melamines alone or with other synthetic or mineral lubricants.

Such other lubricants are, for instance, sebacic acid 2-ethylhexyl ester, nonyl adipate, trimethylol propane tripelargonate, sebacid acid polypropylene glycol ester, dipentaerylthriotol hexapelargonate, 2,4-dibutylamino-6-didodecyl-s-triazine.

The melamines according to the invention are thus suitable for the lubrication of hard surfaces because in contact with these surfaces they form firmly adhesive films thereon, e.g. they are suitable for the lubrication of the surfaces of metals as well as alloys thereof, the surfaces of silicates such as, e.g. of glasses as well as of other materials requiring lubrication such as, e.g., rubber seals.

The N,N',N"-substituted melamines according to the invention can be used alone; however they can also contain additives. Thus, in order to make use of their favourable stability to heat at over C., they are advantageously mixed with antioxidants in order to hinder the autoxidation which occurs above this temperature. The content of antioxidants for this purpose is about 0.015% of the melamines.

Homocyclic or heterocyclic aromatic amines, hydroxysubstituted aromatics, aminohydroxyaryl compounds as well as certain heterocyclic compounds are employed as antioxidants.

Of the amines, in general the secondary monoarnines, in particular the diarylamines having homoand heterocyclic aromatic radicals as well as the aromatic diamines the amine substitutents of which, which are preferably secondary, are in the 0- or advantageously the p-positions, are particularly valuable.

Examples of antioxidants from the class of homoand hetero-cyclic aromatic diarylamines are diphenylamines, phenylnaphthylamines, phenylacenaphthenylamines, 4,4- dinaphthylaminodiphenyl; thiazolyl-(2)-naphthylamines; examples of aromatic diamines are N,N'-diphenyl-p-phenylenediamine, N,N'-dioctyl-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N-sec.butyl-N'-phenyl-pphenylenediamine, N,N' bis-(v-aminopropyl)-p-phenylenediamine.

Of the antioxidants from the class of hydroxyl-substituted aromatics which can be employed in particular at not too high working temperatures (i.e. below 200300 C. depending on type and substratum), those having a sterically hindered hydroxyl group as well as the derivatives of dihydroxyaryl compounds the hydroxyl groups of which are in the 0- or p-position to each other are suitable. Particularly valuable examples of compounds which can be used are the monophenol derivatives such as 2,4-dimethyl-6-tert.butyl phenol,

2,6-di-tert. butyl-4-ethylphenol,

2,6-bis- 1 -methylcyclohexyl) -4-methy1phenol,

2,6-di-tert. butyl-4-dimethylamino-methylphenol,

2,2-methy1ene-bis-(4-methyl-6-tert. butylphenol) 2,2-thio-bis-(4-methyl-6-tert. butylphenol) 4,4-dihydroxy-2,2'-dimethyl-5 ,5 -di-tert. butyl-diphenyl sulphide and diphenyl disulphide,

2,6-bis-(2'-hydroxy-3'-tert. butyl-5-rncthylbenzyl)-4- methylphenol;

derivatives of polynuclear phenols such as 2-tert. butyl-l-hydroxynaphthalene, 4,6-di-tert. butyl-S-hydroxyindane,

5 -hydroxyacenaphthene;

polyvalent phenols and their derivatives; butylpyrocatechine, octyl gallate, hydroquinone, butylhydroxy anisole, hydroquinone monobenzylether.

Of the aminohydroxyaryl compounds, those derivatives having the amino and hydroxyl groups in p-position to each other are particularly suitable as antioxidants. Examples are: p-hydroxydiphenylamine, p-hydroxyoctylaniline, p-hydroxy-N -aminopropylaniline.

Of the heterocyclic antioxidants, the cyclic .imides are the best known; in addition however, heterocyclic compounds containing no nitrogen can be employed provided they are not within the class of heterocyclic amines. Examples are: phenothiazine, iminodibenzyl, 5-ethyl-10, -diphenyl-phenosilazine, 6-methoxyor 6-ethoxyor 6- ethylamino- 2,2,4-trimethyl-1,2-dihydroxyquinoline or the telomers thereof, 3-hydroxy-7,8-benzo-l,2,3,4-tetrahydroqinoline or tocopherol.

In addition, the N,N',N"-substituted melamines according to the invention can contain high pressure additives such as phosphites, phosphates, sulfonates; anticorrosives such as sarcosines or benztriazoles; agents lowering the solidification point, and, possibly, also anti-foaming agents based on silicone.

Also the invention includes lubricating greases produced from the melamine derivatives according to the invention by the addition of the usual thickeners. Examples of such thickeners are metal soaps, bentonite, phthalocyanines, violanthrones, indanthrenes, flavanthrenes, pyranthrones, isatines, indigo.

The following examples illustrate the production and usability of the melamine derivatives having more than one 1,3,5-triazine ring according to the invention. Where not otherwise expressly stated, parts are given as parts by weight. The temperature, where not otherwise indicated, is given in degrees centigrade. The relationship of parts by weight to parts by volume is as that of grammes to millilitres.

EXAMPLE 1 1,6-bis-(2-diethylamino-4'-dibutyl amino-s-triazinyl- (6') -amino) -hexane A mixture consisting of 60 parts of 2-diethylamino-4- dibutylamino-6-chloro-s-triazine (B.P. 138; 11 1.5147) 29.8 parts of 1,6-diaminohexane and 26 parts of pulverised sodium hydroxide is stirred for 4 hours at 120; it is then diluted with 170 parts of xylene and refluxed for another 4 hours. Inorganic components are then filtered off, the filtrate is washed with Water, the xylene is distilled off and the residue is heated for another hour at 240 under 0.5 mm. pressure. 161 parts of 1,6- bis (2-diethylamino 4' dibutylamino-s-triazinyl-(6)- amino)-hexane are obtained as residue. It is a pale yellow mass the refraction index of which is 1.5303. The yield is 93.8% of the theoretical.

Analysis (C H N M.W. 670. Calculated: C, 64.35%; H, 10.43%; N, 25.02%. Found: C, 64.59%; H, 10.68%; N, 24.99%.

The product is a heat-stable, viscous and fatty mass. The dependency of the viscosity on temperature is very favorable for use as lubricant.

8 EXAMPLE 2 N,N'-bis-(2-diethyIamino-4'-dibutylamino-s-triazinyl- (6' -1,8-p-diaminomenthane A mixture consisting of 108 parts of N,N'-bis-(2'-diethylamino 4' chloro s triazinyl (6')-1,8-p-diamino menthane, obtained by reacting 0.5 mole of cyanuric chloride with 1 mole of diethylamine and then with 1 mole of 1,8-p-diaminomenthane, 129 parts of dibutylamine and 10 parts of pulverized sodium hydroxide is stirred for 3 hours at 130, then diluted with parts of xylene andrefiuxed overnight. The solution is clarified by filtration, Washed, the xylene is distilled off and the residue is heated for another hour at 240 under 0.01 mm. pressure. As residue, 124 parts of a tough hard mass which melts at about 40 are obtained. The yield is 86% of the theoretical.

Analysis (C H N M.W.=724. Calculated: C, 66.37%; H, 10.50%; N, 23.20%. Found: C, 66.52%; H, 10.53%; N, 23.37.

At room temperature, the product is hard and wax-like.

The N,N' bis (2'-diethylamino-4'-chloro-s-triazinyl- (6')-l,8-p-diaminomenthane used in this example is produced as follows:

222 parts of cyanuric chloride are dissolved in 700 parts of chlorobenzene and the solution is cooled to -13". 103.3 parts of 1,8-diaminomenthane and 70 parts of water are added dropwise at 5 to 10 within 1 /2 hours. The parts of sodium hydroxide dissolved in 192 parts of water are added dropwise at 5 to 10 within 1 /2 hours. The reaction mixture is neutral after 2 hours. 90 parts of diethyl amine and 90 parts of water are then added dropwise at 2025 followed by 48 parts of sodium hydroxide in 192 parts of water at 20-25 within 50 minutes. The mixture is heated to 40. After half an hour it is neutral. After Working up in the usual way and eliminating all solvents, 286.5 parts of the desired intermediate product are obtained.

The crude product melts at 133139 and is already pure for analytical purposes. The yield is 88.6% of the theoretical. Analysis (C H N Cl M.W. 539. Calculated: C, 53.50%; H, 7.42%; N, 25.90%; Cl, 13.20%. Found: C, 53.75%; H, 7.31%; N, 25.56%; Cl 13.38%.

EXAMPLE 3 N,N'-bis- (2,4-bis-dibutylamino-s-triazinyl- A mixture consisting of 147.6 parts of 2,4-bis-dibutylamino-6-chloro-s-triazine (22 1.5071), 17.30 parts of piperazine and 20 parts of pulverised sodium hydroxide is stirred for 5 hours at then diluted with 200 parts of xylene, and stirred for another 11 hours at Inorganic components are then filtered off and the xylene solution is worked up as described in the previous examples. 144 parts of a yellowish, wax-like mass which melts at 9293 are obtained. The yield is 96.0% of the theoretical.

Calculated: C, Found: C, 67.02%;

65.95%; H, 10.73%; N, 19.65%. H, 10.76%; N, 19.52%.

Similar low melting bismelamines produced other diamines having branched chains which were synthesized, for example, from isosebacic acid and branched chain eicosane dicarboxylic acid. The product has a very good ASTM slope of 0.675 and solidifies only at about 24.

EXAMPLE 6 1 ,4 -bis- [2,4 -bis-dibutylam in0-striazinyl- 6 Found: C, 66.12%;

EXAMPLE 4 1,Z-bis(2,4'-bis-dibutylamino-s-triazinyl-(6' amino)- Z-methylethane A mixture consisting of 14.8 parts of 1,2-propylenediamine 147.8 parts of 2,4-bis-dibutylamino-6-chloro-striazine and parts of pulverised sodium hydroxide is stirred for 4 hours at 120, then diluted with 250 parts of xylene and refluxed for another 10 hours. The product is Worked up as described in Example 1 and finally heated at 230 under 0.02 mm. pressure for minutes. 138 parts of a wax-like mass which melts at 55 are obtained. The yield is 93.3% of the theoretical.

Analysis (C H N M.W.=740. Calculated: C, 66.40%; H, 10.82%; N, 22.68%; CI, 0.0%. Found: C, 65.86%; H, 10.72%; N, 22.46%; Cl, 0.7%.

On heating the wax-like mass obtained at 380, neither acid nor alkaline decomposition products are formed. It is useful as heat transfer agent for heat exchangers operating at l00200.

EXAMPLE 5 N ,N -bz's- [2,4 -bis-dibutylamino-s-triazinyl- (6 ]-1 ,2-di- (w-aminopropoxy -pr0pane A mixture consisting of 29 parts of p-bis-aminomethylcyclohexane, 147 parts of 2,4-bis-dibutylamino-6-chloros-triazine and 20 parts of pulverised sodium hydroxide is stirred for 5 hours at 120, diluted with 200 parts of xylene and then stirred under reflux for another 10 hours. After elimination of the inorganic components the end product is heated for half an hour at 240 under 0.02 mm. pressure. As residue, 151 parts of 1,4-bis-[2',4-bis-dibutylamino-s-triaziny1-(6') -aminomethyl] -cyc1ohexane are obtained. Refraction index: n 1.5238, yield: 93.5% of the theoretical.

Analysis (C H N M.W. 808.5. Calculated: C, 68.40%; H, 10.90%; N, 20.80%. Found: C, 68.38%; H, 10.97%; N, 20.54%.

The product is a viscous, clear mass which is stable to heat.

EXAMPLE 7 1,2-bis-[2,4'-bis-dibutylamino-s-triazinyl-(6)-amin0]- cyclohexane G 4H9 0 H9 A mixture consisting of 147.6 parts of 2,4-bis-dibuty1- amino-6-chloro-s-triazine, 22.4 parts of trans-o-diaminocyclohexane and 20 parts of pulverized sodium hydroxide is stirred for 4 hours at parts of xylene are then added and the whole is refluxed for another 12 hours with stirring. The product obtained is then heated for 1 hour at 240 under 0.01 mm. pressure. 137 parts of a very tough mass are obtained, which corresponds to a yield of 87.9% of the theoretical.

Analysis (C H N M.W. 780. Calculated: C, 67.60%; H, 10.77%; N, 21.55. Found: C, 67.43%; H 10.79%; N, 21.66%.

The product is a viscous mass which is stable to heat,

1 1 1 2 EXAMPLE 8 n 1.5172 are obtained. The yield is 93% of the theoretical. 1,6-bis-(2'-dibutylamin0-4'-octadecylamino-s-triazinyl- Analysis (C H N M.W. 810. Calculated: C, (6')-amin0)-hexane 68.00%; H, 11.12%; N, 20.79%. Found: C, 68.27%;

The product is only very slightly volatile. After heating to 380 for 6 hours, the viscosity measured at 98.9, only alters about 2.34%.

A mixture consisting of 146.2 parts of 2-diethylamino- A m1xture cons1st1ng of 127.5 parts of 2 dtbutylammo p py 35 parts of i i z i g g q g Q3 1: 5: 3 aminohexane and 31.2 parts of pulverised sodium hydrox- Parts t exam an P P ide is stirred for 4 hours at 120, then diluted with 160 Sodium hydroxide are surfed for 6 hours at 2 200 parts of ethyl benzene and stirred under reflux for another parts of xylene are then added and the Whole 1s st1rred 10 hours on Working up as described in Example 1 under reflux for another 6 hoursr on Working up as 152 parts of a product are obtained. M.P. 52-54, yield: scribed in Example 7, 125 parts of a product which melts 95 f {he ttheoreticaL at 7275 are obtained which corresponds to a yield A l i (C H N M W 530 C l l d; C, of 94.2% of the theoretical. 58.82%; H, 9.43%; N, 31.70. Found: C, 58.70%; H,

Analysis (C H N M.W. 1062. Calculated: 9.51%; N, 31.50%. C, 72.30%; H, 11.85%; N, 15.85%, Found: C, 72.07%; The product is very stable to heat and, at room tem- H, 11.91%; N, 16.11%. 35 perawre, is Wax-like.

The product is Wax-like at room temperature and very EXAMPLE 11 stable to heat.

1,6-bis-(2'-hexamethylelzeimino-4'-dibutylamin0-striazinyl- (6 -am ino) -h exam:

CHz-OH -CHt CH -CH -CH CII2C112OH3 /CN\ /NC\ CII2CII2CI*I3 N C-HN CHz NII-O N a r. /C=N \N=C/ 0.119

0 H, oim

EXAMPLE 9 1,6-b is-[2-diethylamin0-4'-(N-methyl-N-dodecylamino)- s-triazz'nyl-(6)-amino]-hexane 6 12 25 1z 25 N N fi A mixture consisting of parts of 1,6-bis-(2'-chloro- 4'-dibutylarnino-s-triazinyl-(6)-arnino)-hexane, 23.9 parts 55 of hexamethyleneimine, 9.2 parts of pulverised sodium 021-1 C=N N=C CzHs hydroxide and 200 parts of xylene is stirred for 8 hours at 140 C. On working up, 63.5 parts of a product of H refraction index n 1.5444 are obtained. The yield is CZHfi 2 88.1% of the theoretical.

A mixture consisting of 158 parts of 2-diethylamino-4- Analysis (CMHNNIZ); 722- Calculated: C, (N- yly 21 parts 66.50%; H, 10.23% N, 23.24%. Found: c, 66.69%; H, of 1,6-diaminohexane and 17.6 parts of pulverised so- 1 41%; N, dium hydroxide is stirred for 4 hours at 120, diluted with The 1 (2c 1 i 4' i 1 120 parts of chlorobenzene and then refluxed for 9 hours. triazinyl-(6')-amino)-hexane obtained is a yellow, greasy On working up, 137 parts of a product of refraction index mass.

'13 EXAMPLE 12 N ,N ',N "-tri- [2,4-bis-dibulylamin-s-triazinyl-(6 dipropylenetriamine 14 Analysis (C H N M.W. 1478. Calculated: C, 66.67%; H, 10.69%; N, 22.88%; Cl, 0.0%. Found: C, 66.87%; H, 10.61%; N, 22.59%; Cl, 0.1%.

A mixture consisting of 19.7 parts of dipropylenetriamine, 166.5 parts of 2,4-bis-dibutylamino-6-chloro-s-triazine and 22 parts of pulverised sodium hydroxide is stirred for 2% hours at 120, diluted with 200 parts of 25 xylene and then stirred under reflux for another 14 hours. On working up as described in Example 1, 146 parts of residue of refraction index n 1.5252 were obtained. The yield is 86.2% of the theoretical.

Analysis (C H N M.W. 1130. Calculated: C, 67.00%; H, 10.78%; N, 22.32%. Found: C, 66.73%; H, 10.79%; N, 22.20%.

The N,N',N-tri- [2,4-bis-dibutylamino-s-triazinyl- 6) dipropylenetriamine obtained is a viscous mass which, in spite of the high molecular weight, only becomes solid at -6.

EXAMPLE 13 triethy lenetetramine EXAMPLE 14 A mixture consisting of 73.9 parts of 2,4-bis-octylamino-6-chloro-s-triazine, 17.2 parts of 1,10-diaminodecane, 10 parts of pulverised sodium hydroxide and 150 parts of xylene is refluxed overnight. After elimination of all inorganic components, the end product is heated at 240 under 0.1 mm. pressure. 78 parts of 1,10-bis- (2',4-octylamino-s-triazinyl-(6)-amino)-decane are obtained. Refraction index 11 1.5218; yield: 93.1% of the theoretical.

A mixture consisting of 21.9 parts of triethylenetetramine, 222 parts of 2,4-bis-dibutylamino-6-chloro-s-triazine and 33.6 parts of pulverised sodium hydroxide is stirred for 4 hours at 120, diluted with 250 parts of xylene and then refluxed for another 10 hours. After elimination of all inorganic components, 221 parts of N,N,N,N"- tetra-[2,4-bis-dibutylamino-s-triazinyl (6)] triethylenetetramine are obtained. It melts between and and Calculated: C, Found: C, 68.73%;

EXAMPLE 15 is a wax-like stable mass having no smell. The yield is Y J -(Q- 99.1% of the theoretical. amino)-3,3'-dimethyl-spiro-diphenylcyclohexane C4H9 04H N CH3 CH3 /N\ 04H) /CN\ /N-C\ C Hg N O-NH 0 NHO/ \N 04 CH \Nzc/ C aH37-NH 2 2 \NH'-C isHs1 A mixture consisting of 58.2 parts of 4,4-bis-(2-chloro- 4 dibutylamino s triazinyl (6) amino) 3,3 dimethyl-spiro-diphenylcyclohexane, 59.2 parts of octadecylamine and 8 parts of pulverised sodium hydroxide is stirred for 20 hours at 160-170. Xylene is added to the Warm reaction mixture and it is Worked up warm. 72 parts of a brown, fatty mass are obtained, which softens at 50 and forms a clear melt at about 95. The yield is 77.5% of the theoretical.

Analysis (C H N M.W. 1240. Calculated: N,

13.52%; c1, 0.0%. Found: N, 13.88%; 01, 0.15%.

The 4,4 bis (2-octadecylamino-4-dibutylamino-s-triazinyl (6) amino) 3,3 dimethyl spiro diphenylcyclohexane obtained is fat-like and, on heating at 380, 15

neither acid nor alkaline products are split off.

N,N',N",N,N"-penta-(2,4-bis-a'ibutylamino-striaziny l- (6 )-te tra-ethylenepentamine EXAMPLE 16 N ,N ',N "-tri- Z-diet/zyam lino-4-dibutylamin0-s triazinyl-(6) )-dihexamezhylenetriamine A mixture consisting of 65.6 parts of dihexamethylenetriamine, 282 parts of 2-diethylamino-4-dibutylamino-6- chloros-triazine and 46 parts of pulverised sodium hydroxide is stirred for 2% hours at 120, then diluted with 320 parts of isopropylbenzene and refluxed for 8 hours. After removal of all inorganic components, the product is heated for minutes at 230 under 0.1 mm. pressure. 282.5 parts of a viscous, fat-like mass are obtained which corresponds to a yield of 89.5% of the theoretical.

Analysis (C H N NW. 1046. Calculated: C, 65.46%; H, 10.52%; N, 24.10%. Found: C, 65.28%; H, 10.54%; N, 24.23%.

EXAMPLE 17 N,N',N"-tri- (2,4-bis-dibutjylamino-s-triazinyl-(6) diethylenetriamine Gib /N\ 04119 I 04119 N ILI A mixture consisting of 19 parts of distilled tetraethylenepentamine, 185 parts of 2,4-bis-dibutylamino-6- chloro-s-triazine and 28 parts of pulverized sodium hydroxide is heated at 120, diluted with 200 parts of ethylbenzene and then stirred under reflux for 16 hours. The reaction mixture is worked up warm and produces 162 parts of pentarnelarnine which becomes soft at room temperature but only forms a clear melt at The yield is 87.7% of the theoretical.

Analysis (C H N M.W. 1854. Calculated: C, 66.14%; H, 10.61%; N, 22.89%; Cl, 0%. Found: C, 66.51%; H, 10.67%; N, 22.63%; Cl, 0.2%.

The product has properties similar to that described in Example 17.

P pane, parts of 2-diethylamino-4-dibutylaminc-6- chloro-s-triazine and 15 parts of pulverized sodium hydroxide is heated at After 3 hours it is diluted with 120 parts of xylene and then stirred under reflux for another 10 hours. Working up produces 77.1 parts of a Calculated: C, Found: C, 65.85%;

EXAMPLE 20 1-(2'-diethylamino-4-dibutylamino-s-triazinyl-(6)-amin0)- 6 [2",4"-bis- (diethylamino) -s-zriazinyl (6) amino]- hexane A mixture consisting of 125.4 parts of 2-diethylamino- 4-dibutylamino-6-chloro-s-triazine, 103 parts of 2,4-bisdiethylamino-6-chloro-s-triazine, 46.4 parts of 1,6-diaminohexane and 38 parts of pulverized sodium hydroxide is stirred for 4 hours at 120, diluted with 270 parts of xylene and then stirred under reflux for another 8 hours. After elimination of all inorganic components and xylene, the product is heated for another 45 minutes under 0.2 mm. pressure.

224.2 parts of l-(2-diethylamin-o 4 dibutylaminos triazinyl (6') amino) 6 [2",4"-bis-(dibutylamino) s triazinyl 6)-amino]-hexane are obtained as residue. It is a pale yellow mass which solidifies at 9. The yield is 91.2% of the theoretical.

Analysis (C H N M.W. 614. Calculated: C, 62.65%; H, 10.01%; N, 27.35%. Found: C, 62.79%; H, 10.10%; N, 26.93%.

The product is stable to heat and there is no a-ppreciable loss of weight on heating for 6 hours at 380.

EXAMPLE 21 1 ,6 -bis- [2'-dimethylamin0-4 (N -phenyl-N -methy amina) -s-triazinyl- (6' -amin] -hexane A mixture consisting of 39.6 parts of 2-dimethylamino- 4 (N phenyl-N-methylamino)-6-chloro-s-triazine, 8.7 parts of 1,6-diaminohexane, 7.2 parts of pulverised sodium hydroxide and 90 parts of xylene is stirred under reflux overnight. After elimination of all organic components, the end product is heated for 1 hour under vacuum of 0.1 mm. Hg at 240. 42.7 parts of 1,6-bi-s-[2'-dimethyl- 18 amino 4' (N-phenyl-N-methylamino)-s-triazinyl-(6)- amino]-hexane are obtained. M.P. 57-60". The yield is 98.2% of the theoretical. Analysis of the crude product, C H N M.W. 390, shows:

Calculated: C, 63.25%; H, 7.35%; N, 29.50%. Found: C, 63.11%; H, 7.63%; N, 29.30%.

The product is heat stable.

Analogous bis-triazine derivatives are obtained if in the above example, the 2-dimethylamino-4-(N-phenyl-N- methylamino)-6-chloro-s-triazine is replaced by equivalent parts of 2-diethylarnino-4-(N-chlorophenyl-N-ethylamino)-6-chloro-s-triazine or 2-dibutylamino-4-(N-xylylor N-toluylor N-dodecylor N-benzylamino, or -N- methylamino or -N-ethylamino)-6-chloro-s-triazine.

EXAMPLE 22 1,2-bis-(2-diethylamino-4'-is0propylamina-striazinyl-(6)-amino)-ethane Analysis (C H N M.W. 452. Calculated: C, 55.75%; H, 8.94%; N, 35.40%. Found: C, 55.76%; H,

The product has no smell and is heat stable.

Analogous bis-s-triazine derivatives are obtained if in the above example, 1,2-diaminoethane is replaced by equivalent parts of 1,4-diaminobutene-2 or 1,2-diaminopropane or 1,20-diaminoeicosane.

EXAMPLE 23 E ca-NH A mixture consisting of 121 parts of 2,4-bis-ethylamino- 6-chloro-s-triazine, 18.1 parts of 1,2-diaminoethane, 18.4 parts of pulverised sodium hydroxide and 300 parts of xylene is refluxed overnight while stirring. After elimination of all inorganic components, the end product is heated for 1 hour at 230 under 0.01 mm. Hg. 107 parts 1 9 of 1,2 bis-(2,4'-bis-ethylamino-s-triazinyl-(6')-amino)- ethane, a yield of 91.2%, are obtained. The product so isolated is pure enough for analysis as can be seen from the elementary analysis. M.P. 88-90".

Analysis (C H N M.W. 390. Calculated: C, 49.35%; H, 7.70%; N, 43.00%. Found: C, 49.24%; H, 7.80%; N, 42.67%.

Analogous bis-triazine derivatives are obtained if in the above example instead of 2,4-bis-ethylamino-6-chloros-triazine, equivalent parts of 2,4-bis-allylamino-6-chloros-triazine or 2,4-bis-octadecenylamino-6-ch1oro-s-triazine are used. Also the 1,2-diaminoethane can be replaced by equivalent amounts of 1,2-diaminopropane.

EXAMPLE 24 1 ,6 -bis-( 2 ,4 '-bis-dimethylamino-s-triaziny l- 6 amin)-hexane A mixture consisting of 80.6 parts of 2,4-bis-din1ethylamino-'6-chloro-s-triazine, 23.2 parts of 1,6-diaminol1exane, 19.2 parts of pulverised sodium hydroxide and 120 parts of xylene is stirred under reflux overnight. All inorganic components are eliminated by dilution with chloroform. The end product is heated for 1 hour at 230 under 0.01 mm. Hg. A residue of 83.7 parts of 1,6-bis (2,4 bis dimethylamino s triazinyl (6)- amino)-hexane is obtained. M.P. 165-166". Yield 93.7%. The product is already 'sufiiciently pure for analysis as can be seen from the elementary analysis:

Analysis (C H N M.W. 446. Calculated: C, 53.70%; H, 8.52%; N, 37.67%. Found: C, 53.67%; H, 8.59%; N, 37.54%.

An analogous bis-s-triazine derivative is obtained if in the above example the 2,4-bis-dimethylamino-6-chloro-striazine is replaced by equivalent parts of 2-diisobutenylamino-4 dimethylamino-6 chloro-s-t-riazine. Also, the 1,6-diaminohexane can be replaced by equivalent parts of 1,18-diaminooctadecane.

EXAMPLE 25 1,2-bis-(2',4-bis-dimethylamino-s-triazinyl- (6 -amin0ethane A mixture consisting of 50.8 parts of 2,4-bis-dimethylamino-6-chloro-s-triazine, 7.6 parts of 1,2-diaminoethane, 12 parts of pulverised sodium hydroxide and parts of xylene are stirred under reflux overnight, then diluted with chloroform and all inorganic components are eliminated. The end product is heated for 1 hour at 230 under 0.01 mm. Hg. 45.2 parts of 1,2-bis-(2',4'-bis-d-imethylamino-s-triazinyl-(6')-amino)ethane are obtained as distillation residue. Yield 92.3%. M.P. (recrystallised from ethanol) 210-211".

Analysis (C H N M.W. 390. Calculated: C, 49.25%; H, 7.69%; N, 43.15%. Found; C, 49.41%; H, 7.87%; N, 43.00%.

Analogous bis-s-triazine derivatives are obtained if in the above example the 2,4-bis-dimethylamino-6-chloro-striazine is replaced by equivalent parts of 2-diallylamino- 4-dimethylamino-6-chloro-s-triazine or Z-dimethylamino- 4-dioctylamino-6-ohloro-s-triazine. Also the 1,2-diaminoethane can be replaced by equivalent amounts of 1,2-diaminopropane.

When great quantities are used, in some cases the condensation between monochlorotriazines and amines is rather exothermic. In example 28 of the following Table I for example, 1007.5 parts of 2,4-bis-ethylamino-6-chloro-s-triazine were stirred with 296 parts of 1,6-diaminohexane and 250 parts of sodium hydroxide. Due to the exothermic reaction, in spite of exterior cooling with ice water, the reaction temperature rose within a short time to 172. Thus the condensation was completed in a relatively short time.

Condensation with exclusion of oxygen leads to considerably lighter coloured end products.

The following Table I contains further examples of N,N',N-substituted melamine derivatives according to the invention of the general formula which are obtained by reacting cyanuric chloride in steps with the primary and secondary organic monoamines corresponding to X and Y and with the primary and secondary dia-mines corresponding to Z as fully described in Example 1. Column 5 of Table I shows the yield attained in the last step in percent of the theoretical, column 6 gives the molecular weight and column 7 the solidification point.

In the following Table Ia, column 2 contains the formula of the compounds given in Table "I, and columns 3 to 8 show the results of elementary analysis for carbon, hydrogen and nitrogen compared with the theoretical content.

TABLE I No. X Y Z Percent MW solidification point 26 N(C2H5)n N(C2H5)2 HN(CH2) flNH 90. 558 ViSCOllS HNC2H5 HNCzHu HN(CH2)6NH 95.3 446 90 N(C4Ha)z N(C4II9)g HNwHmNH 85.0 782 4 N(C4H N(CHa)z HN(CH)5NH 88.9 614 N (Cd-Ia) z N CiHg) 2 EN CH ENE 94. 2 810 13 N(C2H5)2 N(C2H5)z HN(CH;)10NH 88.2 614 14 N(C4Hg)2 N(C4Hn)q HNOHzCHzOCHzCHa 89.3 814 11 HN C H2 C H2 0 33 N o 4H9) i N 04H.) 1 HN H OHz-@NH 98.2 876 34 N (041 1) 2 N (04H!)) 2 N-CHnCHz-N 98. 1 838 76-78 C4 n C4Ho 35 N(C4Hn)z N(Cig1137)2 HN(CH2)6NH 94. 7 1,566 2 36 N(C4Ha)2 N(C2H5)z HNCHzCHaNH 87.6 614 +59 CH7 CH 37 N\ )CHQ N (CHEM HN(OH2)BNH 88.9 606 M.P. 198

CH CH TABLE 1a Analysis, percent N0. Formula C H N Caleu- Found Calcu- Found Oa1cu- Found lated lated lated Table II shows the physical data of the compounds from which the stability of the melamine derivatives according to the invention at high temperature and their viscosity behaviour can be seen. Columns 2 and 3 give the viscosity measured at 100 F. (=37.8 C.) and 210 F. (989 C.), and column 4 shows the so-called ASTM slope.

The meaning of the ASTM slope is as follows: If in a co-ordinate system, the temperature (in degrees Fahrenheit) is given as the abscissa and the natural log of the viscosity (in centistokes) is given as ordinate, then a plot is formed which, for practical purposes, can be regarded as straight. Thus the viscosity for the whole temperature range can be interpolated from two points determined by experiment (conventionally the viscosities at 100 F. and 210 F. are determined). The slope of this plot is a standard for the dependency of the viscosity on temperature. Therefore, the ASTM slope is the quotient of the ordinate over the abscissa of the two points measured in cm. which are obtained by plotting the actual viscosity values at various temperatures in the ASTM chart. The ASTM Standard Viscosity-Temperature Charts for Liquid Petroleum Products (Method B 341) are standard graphs which are in close resemblance to the co-ordinate system described above. ASTM is an abbreviation for American Society for Testing Materials, 1916, Race Street, Philadelphia, Pa.

Columns 5 and 6 show the loss in weight in percentage within 6 hours incurred by a sample of 25 c.c.m. on heating to 380 or 400 C. in a glass test tube of about 25 mm. diameter with simultaneous introduction of nitrogen (2 litres per hour).

Column 7 shows the alteration in the viscosity in percentage measured at 210 F. incurred by the sample on heating for 6 hours as described above.

TABLE II Viscosity in Loss in Percentage centlstokes at weight after of viscosity N0. ASTM 6 hours atalteration a slope after 6 hours F 210 F. in centistokes (378 C (98.8" 0.) C. Percent at 210 F.

TABLE II Viscosity in Loss in Percentage centistokes atweight after of viscosity No. ASTM 6 hours at alteration slope after 6 hours 100 F. 210 F. in centistokes (37.8 C.) (98.8 C.) C. Percent at 210 F.

EXAMPLE 38 50 parts of the compound of Example 1 which has a viscosity of 12.160 centistokes at 37.8 and 120.9 centistokes at 988 are stirred with 50 parts of a polypropylene glycol sebacic acid ester (Reoplex 100 marketed by The Geigy Co. Limited, Manchester, England). The mixture has the good lubricant properties of the components and the viscosity of the mixture is 6.263 centistokes at 37.8 and 265 centistokes at 98.8. From this the ASTM slope is calculated at 0.492.

The application possibilities of the melamine compounds used are considerably broadened by this reduction of the ASTM slope.

EXAMPLE 39 3 parts of copper phthalocyanine are stirred in c.c.m. of benzene in an Ultraturax mixing apparatus (Janke & Kunkel, Stauffen, Baden, Germany). 9 parts of the mixture obtained according to Example 1 are slowly added to this mixture and the whole is stirred for 45 minutes. The homogeneous mass so obtained is worked on a glass surface with a spatula until the excess benzene has evaporated.

The mass obtained is heated for 45 minutes at 150 and, after cooling, is again worked with a spatula.

A good grease which can be well worked is obtained.

EXAMPLE 40 99 parts of the compound according to Example 24 of Table I and 1 part of iminodibenzyl are stirred together until the latter has completely dissolved. The mixture obtained has improved stability to oxidation when compared with the pure triazine compound.

Similar results are obtained if instead of the above compound, the other synthesised compounds mentioned in this document are used with the usual antioxidants most useful for the intended purpose in amounts of 0.01 to 5%.

EXAMPLE 41 The lubricity of a representative lubricant according to the invention and that of four different synthetic lubricants commercially available (used as comparison) was measured in a Precision Shell four ball apparatus. This apparatus ran for minutes at a speed of 1480 revolutions per minute with a load of kg., using /2 inch steel balls SKF A-quality. The starting temperature was 22 C. The results are summarised in the following table:

24 TABLE III Substance used: Diameter of abrasion calotte in mm. Example No. 1 0.612 Di-3,5,5-trimethyl-hexy1-sebaceate 0.817 Di-2-ethylhexyl-sebaceate 0.850 Di-Z-ethylhexyl-adipate 0.915 Methylphenyl silicone (MS 550 of Midland Silicones Ltd.) 1,953 (In this test there was no lubrication even after 2 /2 minutes) Each of the above values is the average of three tests.

What we claim is: 1. A lubricant composition for use in engines operating at elevated temperatures containing as the essential lubricating ingredient a compound of the formula \R4 11 wherein A is an n-valent polyamine radical having from n to 20 carbon atoms and a total of from 2 to 5 nitrogen atoms, all of which are acylatable and are separated from each other by at least two carbon atoms, and being selected from the class consisting of the radicals of (a) saturated aliphatic chain-linked, cyclic and mixed aliphatic chain-linked-and-cyclic polyamines, (b) saturated aliphatic chain-linked aliphatic polyamines which contain oxygen in the chain, and (c) phenyl-cyclohexylene-phenyl-diamines, n is a positive integer ranging from 2 to 5, each righthand moiety in the above formula being linked to one of said acylatable nitrogen atoms of A, each of R and R is, independently of the other, a

member selected from the group consisting of hydrogen, alkyl with maximally 18 carbon atoms,

each of R and R is, independently of the other, a

member selected from the group consisting of alkyl with maximally 18 carbon atoms, monocyclic aralkyl in which the alkylene bridge has maximally 4 carbon atoms, phenyl, chlorophenyl, fluorophenyl, bromophenyl and alkylphenyl in which alkyl has maximally 12 carbon atoms, and

R and R as well as R and R when taken together with the nitrogen to which they are attached can be a member selected from the group consisting of tetramethyleneimino, pentamethyleneimino, hexamethyleneimino, morpholino or n-methylpiperazino radical, and another lubricant selected from the group consisting of mineral oils, synthetic ester lubricating oils, and silicone oils, said other lubricant being present in said composition in an amount of 0 to about 50% by weight thereof, and about 0.01 to about 5% by weight, calculated on the weight of the composition, of an antioxidant selected from the group consisting of homocyclic aromatic amines, hydroxy-substituted aromatic compounds, aminohydroxyaryl compounds and heterocyclic antioxidants.

2. A lubricant composition as defined by the formula of claim 1, wherein said other lubricant is a member selected from the group consisting of the sebacic acid ethyl-hexyl ester, nonyl adipate, trimethylolpropanetripelargonate, sebacic acid polypropylene glycol ester, dipentaerythritol hexapelargonate and 2,4-dibutylamino- 6-didodecyl-s-triazine.

3. A lubricant composition for use in engines operating at elevated temperatures consisting essentially of a compound as defined by the formula of claim 1 and from about 0.01 to by weight calculated on the weight of the composition, of an iminodibenzyl.

4. A grease composition for use in engines operating at elevated temperatures consisting essentially of from about 50 to 85% by weight, calculated on the total weight of the composition, of a component liquid at room temperature which consists of at least one compound as defined by the formula of claim 1, the balance consisting essentially of a thickener selected from the group consisting of metal soaps, bentonite, phthalocyanines, violanthrones, indanthrenes, flavanthrenes, pyranthrones, isatines and indigo.

5. A lubricant composition for use in engines operating at elevated temperatures containing as an essential lubricating ingredient, in an amount sufficient to render the composition a lubricant, a compound of the formula wherein A is an n-valent polyamine radical having from n to 20 carbon atoms and a total of from 2 to 5 nitrogen atoms, all of which are acylatable and are separated from each other by at least two carbon atoms, and being selected from the class consisting of the radicals of (a) saturated aliphatic chain-linked, cyclic and mixed aliphatic chain-linked-and-cyclic polyamines,

(b) saturated aliphatic chain-linked aliphatic polyamines which contain oxygen in the chain, and (c) phenyl-cyclohexylene-phenyl-diamines, n is a positive integer ranging from 2 to 5 each right- 5 hand moiety in the above formula being linked to one of said acylatable nitrogen atoms of A, each of R and R is, independently of the other, a

member selected from the group consisting of hydrogen, alkyl with maximally 18 carbon atoms, each of R and R is, independently of the other, a member selected from the group consisting of alkyl with maximally 18 carbon atoms, monocyclic aralkyl in which the alkylene bridge has maximally 4 carbon atoms, phenyl, chlorophenyl, fiuorophenyl, brornophenyl and a-lkylphenyl in which alkyl has maximally 12 carbon atoms, and R and R as well as R and R when taken together with the nitrogen to which they are attached can be a member selected from the group consisting of tetramethyleneimino, pentamethyleneimino, hexamethyleneimino, morpholino or n-methylpiperazino radical, and from about 0.01 to about 5% by weight calculated on the weight of the composition of an antioxidant selected from the group consisting of homocyclic aromatic amines, hydroxy-substituted aromatic compounds, aminohydroxyaryl compounds and heterocyclic antioxidants.

References Cited by the Examiner UNITED STATES PATENTS 4/1936 Semon 25250 5/1961 Halter et al 25251.5 X 4/1962 Wilson 25218 6/1962 Dess 25251 X 9/1965 Lutwack 252-47 X 

1. A LUBRICANT COMPOSITION FOR USE IN ENGINES OPERATING AT ELEVATED TEMPERATURES CONTAINING AS THE ESSENTIAL LUBRICATING INGREDIENT A COMPOUND OF THE FORMULA 